Applications of New Concepts of Physical-Chemical

Wastewater Treatment
Sept.18-22, 1972

CHEMICAL REGENERATION OF ACTIVATED CARBON

J.M. ROVEL
Direction Technique Degreraont France

The Table (Fig. 1) below is derived mainly from a study-

made by Mr, F.P. Sebas ti an (l) and shows, as a function of the
quantity of pollutants to be eliminated (g of COD/1) under the
current price conditions applicable in the U.S.A., the various
factors affecting the cost for the treatment of water on
activated carbon, whether or not such treatment would include a
thermal regeneration unit.

TABLE
FIG. 1

Installations 1 MGD
All Costs in Cents/lToOO g

Elimi- Carbon Furnace Make M.O. Total Total Incidence

nated + (capi-
up power cost cost of ]
COD adsor- carbon fuel with with Furn- Make i
tal)*
U/m3) bers out regen ace up
(896)
(capi- regen cap. (#)
tal)* <*)

180 1.7 2.2 3.95 1.5 51 9.3k 23.5 k2 I

80 1 .82 2.35 1.75 1.73 2k.k3 7.66 31 23
20 1.85 2.35 0.45 1.51 7.93 6.16 38 7.1

* 6$ - 25 years

187
188 J. M. ROVEL

Prom this table we see that :

- The use of lost carbon is out of economics as soon as we leave
the field of potable water
- With thermal regeneration the major elements of the cost are:-

• Carbon addition (calculated at 8$ per regeneration)

• Amortization of the regeneration furnace.

The interest of searching for a process improving both

factors is thus evident. This is why Degr&nont has been studying
this problem for 2 years and developed a process covered in
France by the patents:-

- No 2 094 336 registered : 17th June 1970

- No 2 042 212 registered : 20th June 1970
and in the U.S.A., by the patent:-
- No 47 599

I - Conducting the Research Vork

It has long been recognized that:-

(a) The lower the pH value, the better most of the organic
molecules adsorb together

(b) Regenerations (at least partial) were made by means of hot

caustic soda (desorption of phenols in particular).

Besides, the study of these mechanisms showed us that, in

addition to the adsorption process modifications due to an
inversion in the polarity of carbon surface oxides, soda also
provokes an hydrolysis of some compounds (amino acids...).

Since this action was not complete, we tried to combine it

with the action of a solvent which, to be satisfactory, had to
possess the following qualities:-

- Important solvation power with large spectrum

- Adsorption power in alkaline medium in order to displace the

substances worse adsorbed than it in this pH range

- Easily eluted, in particular under the action of vapour (thus

involving a low boiling point and a very low adsorption
capacity in neutral medium)

- Low cost and easy recovery from the eluate

 Chemical Regeneration of Activated Carbon 189

A study of numerous systems of solvents (alcohol,

chlorinated solvents, DMF, e t c . . ) was made using in particular
a microcalorimeter which enabled us to estimate, from the
measurements of adsorption temperatures, the affinity of the
various solvents for carbon, as a function of ambiental
conditions (temperature, pH . . ) •

Thanks to this study, we could select the isopropyl alcohol

as meeting the best of all the above criteria.

Besides, we checked over a wide range of examples that the

use of soda and alcohol in combination, as described below,
enables to eluate most of the products adsorbed on a carbon more
completely than with any of both components used separately or
combined.

II - Description of the Degremont Process

It includes 5 main stages, 2 of them optional (1 and 5) •

(1) Initial treatment by acid, intended to eliminate any mineral

gang which would have deposited on carbon during fixation.

- 0.5 to 1 volume of solution of HC1 at 1 to 2$ (which can

be re-used several times) - Duration : 1 hour.

(2) Hot treatment (heating by vapour at 100 - 110° C) by a soda

solution at 10$, allowing carbon to macerate during 1 hour.

- 1.25 volume of soda 10$ - Total time 2\ hours.

(3) Injection of a solvent at the top of the column and very

slow percolation through the bed at 80° C.

- 0.5 volume of solution at 50$ alcohol - Duration : 3 - ^

hours.

(k) Evaporation (120 - lk0° C) - Duration : 1 hour, i.e. 0.75 to

1 kg of vapour per kg of carbon.

(5) If required, re-acidification of carbon before use

- Solution with 1 to 2$ HC1 - 10 mn

The sodic and alcoholic effluents are stored then:-

- 90 to 95$ of the alcohol is recovered through

distillation.
190 J. M. ROVEL

- The sodic effluent and the solids on the bottom of the tank
of the previous distillation are either rejected after
neutralization or, more currently, concentrated and
brought to 500° in order to obtain an alkaline fusion;
during this operation, the organic matter is pyrolised,
producing an easily sedimented coke and gases which are
re-introduced into furnace burner.
The recovered soda (5% losses appr.) is put again into a
solution for the next regeneration. It contains only 50 to
100 mg/1 of COD.

Ill - Performing the Regeneration

Two procedures can be applied:-

(1) Semi-mobile beds

The sketch at Fig. 2 below shows the major components of

sucji a*iinstallation: -

The fixation column (l), the regeneration column (2),

a water/alcohol separator (3)t a condenser (5) f a reagent
storage unit (6), a reagent heating exchanger (4) and the
alkali fusion tank (7).

Part of the carbon is transferred hydraulically to the

regeneration tank. After passing through the said tank, the
carbon is re-injected on top of the contact bed; the tank itself
is used later as distillator for the alcoholic phase and as
concentrator for the sodic phase.

(2) Fixed beds

In this example : fixation columns manufactured in order

to allow in situ regeneration of the carbon (stainless steel
made, rated at 3 bars with the necessary valves and fittings
for reagent inlet and outlet, thermal insulation).
Usually three columns will be used which can be regenerated
alternatively and put back into operation in the third position.

Though heavier from an investment point of view, this

process presents the great advantages of:-

- Involving no carbon transfer, hence no losses by attrition

- Requiring labour only at the regeneration stage, i.e. one

work post per column to be regenerated
Chemical Regeneration of Activated Carbon 191

Fjgur# 2

•t«a»
192 J. M. ROVEL

IV - Example of Application t Pilot Study for

a PTBB Acid Production Shop

One of the shops at the Cuise Lamotte Factory of the

NOBEL BOZEL Company synthetizes the PTBB (para-tertio-butyl-benzic
acid) through oxidation of the tertio-butyl-benzene by nitric
acid,

The effluent rejected by this shop contains numerous

aromatic nitrated by-products and is featured by:-

- Output 12 m3/h
- COD 1700 to 2000 mg/1
average value : 1800
- Colour strong yellow still noticeable
after dilution in 100 volumes
of clear water,
Since the main components of this effluent were not
biodegradable, an adsorption treatment became necessary. The
preliminary tests showed that a treatment on carbon did not
allow to economically reduce the COD until obtaining an effluent
which can be directly discharged but that under proper conditions
it allowed to eliminate 60 to 70$ of the COD and all the
coloured components.

Therefore, a pilot unit has been installed in this factory

and two series of tests were carried out:-

(a) Utilization of a fixation column on semi-fluidised beds,

containing 230 litres of Pittsburgh carbon and a kZ litre
regenerating column,

The following Table shows the results obtained with a

fixation velocity : 250 l/h (retention time 55 mn) and two
carbon renewing speeds:-

- Tests 1 to 10 with 1 regeneration i.e. kZ l/d

- Tests 11 to 18 with 1 regeneration i.e. k2 1 every other day

 Chemical Regeneration of Activated Carbon 193

TABLE
FPT7~3

Test No. Treated Volume COD mg/l of 0 2

1 5,250 1 310
2 5,250 1 380
5,250 1 385
4 5,250 1 685
5 1 5,250 1 640
6 1 5,250 1 I 570
7 i 5,250 1 525
8 5,250 1 470
9 5,250 1 550
10 5,250 1 465

11 10,500 1 670
12 5,950 1
13 10,500 l 730
14 10,500 1 j 635
15 10,500 i 560
16 10,500 1 550
17 10,500 i 580
18 10,500 1 660
1
One should note that after 18 cycles the carbon has been
regenerated 3^3 times and that if a visible COD increase appears
for cycles 1 to 5 which correspond to the time to reach the
column normal operation conditions (regeneration of 210 1 on
230 l ) , then the performances remain very stable and the
obtained capacity is excellent:-
- Average for tests 11 to 18:-

. COD at the inlet 1,800 mg/l

. COD at the outlet 625 nig/l
i.e. 1*18 kg of COD fixed by treated cubic meter or 615 g COD
by kilo of saturated carbon.
194 J. M. ROVEL

(b) Utilization of a column with 6.6 1 fixed beds (0 80 mm)

to be able to check the constancy of the result on a
greater number of regenerations,

In this case, the retention time was shorter (25 nun, i.e.
15 l/h) which explains that on a average the results in the
following Table correspond to a smaller capacity than those
obtained in the previous test:-

TABLE
FIG, k

No. Vol. cycle Velocity COD after End of Colouration

(1) (iA) 300 1 cycle

1 291 15 250 Nil

2 600 15 150 500 n I
3 437 15 400 n 1
4 500 15 200 420 n I
463 15 400 II I
5 it j
6 787 29. 780
7 1070 29. 1300 pale yellow
8 903 20 400 1300 yellow
9 685 15 50 300 trace
10 531 15 310 1000 yellow
11 500 15 270 400 Nil
12 350 270 400 ff I
15
500 250 500 tf I
13 | 15

It has been established that after a stabilization

obtained on the first 5 cycles, an attempt to increase the
velocity to 30 l/h (12 mn of retention time) showed a rapid
colouration leakage which entailed perturbations until the
10th cycle.
On the contrary the last three cycles have performances
close to those shown for the first five.
However, it shows a slight capacity decrease which
corresponds to 10 to 15% approx. of the initial capacity. Yet,
one must note that no carbon was added during these 13 cycles
and that the total carbon lost by dragging small carbon is
lower than 10%.

The regeneration eluate analysis shows that the maximum

pollution is extracted from coal when the solvant injection
begins (see curves Fig. 5 ) •
 Chemical Regeneration of Activated Carbon 195

The above results and other obtained from similar experiments run
on other type of industrial waste waters, such as :

- pharmaceutical wastes (at Roussel Uclaf Vertolaye plant)

- beet sugar juice for discolouration treatment (at Sucreries du
Soissonnais)
- textile wastes such as bleaching and printing sections (at
Teintureries Steinheil Dieterlen in Rothau)

have disclosed the efficiency of the proposed regeneration process

they lead us to conclude that the best regeneration proceedure is
always the application of caustic soda followed by alcohol for it
restore at least 80 $ of the initial capacity of the carbon.

V - ECONOMICS

Table (fig# 6) summarizes the economics of plants designed for the

regeneration of 10 m3/dayf with application of either chemical or
thermal proceedures.

Costs of chemicals and other entries are expressed in french fraixs

per one cm3 of treated carbon.

Figure 6
Chemical regeneration Thermal regeneration

Investment costs
- All needed equip* 350.000 F -Furnace 430.000 F
- Boiler (if no vapor -Accessories (storage
available locally) 50.000 F drainage, transfert
- Soda melter 50.000 F l i n e , regulations,
mounting) 550*000 F
450.000 F 980.000 F

Running costs
reagents
-Caustic(l) 6,2kg 0f32F/kg 2 F
-Fuel (1) 450kg 0f12F/kg 5k P
-Alcohol(2) 16kg 0,80F/kg 12, 8 F
-Steam (heating +
displacement) 40 F t\J 100 F
-Softened water 2, 7 F
Labor 20 F
Carbon Make up
2 # = 20 1 x 2 f 2 5 k5 F - 8 # = 80 1 180 F

176,5 F 280 F
196 J. M. ROVEL

(1) If caustic effluent can be wasted - no fuel needed but we used

125 kg of caustic soda = 40 F (cost reduced by 14 P)
(2) Assumption : 90$ recovery by distillation.

It appears that not only prime costs are 50$> cleaper but also
running cost are some what 35$t lower.

In addition to these essential conclusions it can be said that for

small plants I up to 5 m3 day of regenerated carbon, labor costs
are even more favorable as the plant can be designed such as to be
operated only every few days (in situ regeneration) meanwhile
thermal regeneration requires always a continuous operation and
care.

We see other advantages such as an easier temperature control and

also the fact that final wastes of the plant do not contain any
toxic chemical. The latter remark is to be opposed to the large
amount of CO gas which is released to the atmosphere by furnaces.

It is also avoided that inert chemicals (such as iron, alcaline

salt compounds...) which eventualy during thermal process would
melt and cause the activated carbon grains to aggregate with
subsequent carbon loss and troubles.

More over following factors would be mandatory for the use of

chemical regeneration; such as :

- The possibility of using low grade (mechanical characteristics)

activated carbon of low price such as NORIT PKST which
nevertheless has been effectively regenerated up to 3 times
during our experiments.

- Special industry wastes containing nitrate compounds (see

above NOBEL BOZEL wastes) which can be found also in synthetic
dies or polyurethane industries, and would create explosion
hazards if brought to elevated temperatures.

However for the time being all applications of this chemical rege-
ration process are not yet all investigated and we must admit that
there would be some instances where refractory chemicals present
in the water would offer strong affinities to carbon and hamper
the efficiency of this chemical regeneration process.

This is the reason why we feel that preliminary survey must be

performed over any specific effluent to be treated in order to
determine whether this proceedure is applicable or not.
 Chemical Regeneration of Activated Carbon 197

Conclusions

The economic survey as expanded here above, and the favourable

results obtained for some specific effluents show that this
chemical regeneration process is promised to a brilliant future
and that it will help to minimize the actual treatment costs
which, at least presently in Europe, confine the use of activated
carbon to very specific cases.

Ref. (l) FoP. Sebastian (Envirotech) - Water & Waste Treatment

(May, 72)

Fig* 5 : Typical regeneration of h2 saturated carbon -

A Co
I 1

'/A
I i
l I •
/
I
i.
i
i

A-r\

r
r•
I

-r— «—• 1 k->

-1* 20 30 40 50 60 70 1 eluate
Concentration in NaOH

Pollutants concentration
Alcohol concentration
alcohol Steam
injection injection